Abstract

Photoreaction of molecular complex composed of ozone and dimethylamine is investigated by matrix-isolation IR and UV–visible spectroscopies. The UV–visible spectrum of the molecular complex isolated in an Ar matrix shows two broad bands in the region between 400 and 700 nm. Upon red-light irradiation (λ ≥ 680 nm), dimethylamine-N-oxide is produced by intermolecular oxygen-atom transfer from O3 to the lone pair on the nitrogen atom of dimethylamine. Dimethylamine-N-oxide isomerizes to N,N-dimethylhydroxylamine by intramolecular hydrogen-atom migration upon the second light irradiation (λ ≥ 385 nm). The both photoproducts are identified by the DFT calculation at the B3LYP/6-31++G(d,p) level.

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